Industrial processes of lignocellulosic material have made use of only the hexose component of the cellulose fraction. Pentoses and some minor hexoses present in the hemicellulose fraction, which may represent as much as 40% of lignocellulosic biomass, have in most cases been wasted. The lack of good methods for utilization of hemicellulose sugars is a key obstacle hindering the development of lignocellulose-based ethanol and other biofuels. In this chapter, we focus on the utilization of hemicellulose sugars, the structure of hemicellulose and its hydrolysis, and the biochemistry and process technology involved in their conversion to valuable fuels and chemicals.